CN115558112B - Low-migration silicon-containing macromolecular photoinitiator and preparation method and application thereof - Google Patents
Low-migration silicon-containing macromolecular photoinitiator and preparation method and application thereof Download PDFInfo
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- CN115558112B CN115558112B CN202110750469.7A CN202110750469A CN115558112B CN 115558112 B CN115558112 B CN 115558112B CN 202110750469 A CN202110750469 A CN 202110750469A CN 115558112 B CN115558112 B CN 115558112B
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- photoinitiator
- silicon
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- acrylate
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 69
- 239000010703 silicon Substances 0.000 title claims abstract description 69
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000013508 migration Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 8
- -1 silicon acrylic ester Chemical class 0.000 claims abstract description 56
- 238000000016 photochemical curing Methods 0.000 claims abstract description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000005012 migration Effects 0.000 claims abstract description 19
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 16
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 16
- 239000003085 diluting agent Substances 0.000 claims abstract description 9
- 150000003254 radicals Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 36
- 239000012948 isocyanate Substances 0.000 claims description 34
- 150000002513 isocyanates Chemical class 0.000 claims description 33
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 26
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 25
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 16
- 239000000376 reactant Substances 0.000 claims description 13
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 12
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 12
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 11
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 9
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 8
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 7
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 7
- 238000006482 condensation reaction Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- KSWLTWDBKKOLQA-UHFFFAOYSA-N 2-(1-hydroxycyclohexyl)-1-phenylpropan-1-one Chemical compound C1CCCCC1(O)C(C)C(=O)C1=CC=CC=C1 KSWLTWDBKKOLQA-UHFFFAOYSA-N 0.000 claims description 4
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims description 4
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- DSSXKBBEJCDMBT-UHFFFAOYSA-M lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O DSSXKBBEJCDMBT-UHFFFAOYSA-M 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 claims description 2
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 2
- 229920006305 unsaturated polyester Polymers 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 20
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 19
- 238000001816 cooling Methods 0.000 description 10
- 238000002390 rotary evaporation Methods 0.000 description 10
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 8
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 4
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002026 chloroform extract Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention belongs to the field of photo-curing, and discloses a low-migration silicon-containing macromolecular photoinitiator, and a preparation method and application thereof. The invention makes the photoinitiator become a silicon-containing macromolecular photoinitiator by grafting the photoinitiator onto the organic silicon acrylic ester. The silicon-containing macromolecular photoinitiator is suitable for a free radical photo-curing system, and can initiate common acrylic ester reactive diluents and various acrylic resins. The silicon-containing macromolecular photoinitiator is provided with a plurality of acrylate groups, so that the silicon-containing macromolecular photoinitiator can participate in the photocuring process, and the migration problem of the common photoinitiator is solved. Meanwhile, the organic silicon is introduced into the photo-curing system, so that the hydrophobicity and heat resistance of the photo-curing film can be improved.
Description
Technical Field
The invention belongs to the field of photo-curing, and particularly relates to a low-migration silicon-containing macromolecular photoinitiator, and a preparation method and application thereof.
Background
The photocuring technology is a surface treatment technology for quickly polymerizing and crosslinking liquid materials with chemical activity by ultraviolet light and instantly curing the liquid materials into solid materials, has the advantages of economy, high efficiency, wide adaptability, energy conservation, environmental protection and the like, is known as a new technology in the 21 st century green industry, and is widely applied to the fields of printing, packaging, advertising, building materials, electronics, computers, aerospace and the like.
The photocuring system mainly comprises a prepolymer, a diluent and a photoinitiator. The prepolymer and diluent contain UV curable acrylate groups or epoxy groups that are capable of participating in a photocuring reaction during photocuring to form part of a crosslinked network. The photoinitiator used at present does not contain the groups, and most of the photoinitiators are small organic molecules, the residual photoinitiators are easy to migrate to the surface of the coating in the photocuring process, meanwhile, peculiar smell, yellowing and toxicity can be generated, the appearance and the performance of the coating are influenced, and the application range of the photocuring product is limited, particularly in the fields of sanitation, food packaging and the like.
In order to solve the problem of high migration of the existing photoinitiator, the photoinitiator can be grafted onto a polymer or an unsaturated group capable of being cured by Ultraviolet (UV) is introduced into a small-molecule photoinitiator, so that the photoinitiator can participate in the photo-curing process, and the migration problem of residual photoinitiator in the photo-curing process is improved.
Chinese patent publication CN109721691a discloses a single-component polysiloxane photoinitiator capable of overcoming oxygen inhibition, which is a photoinitiator introduced on a side chain of hydrogen-containing polyoxy silane and retains a certain amount of silicon hydrogen bonds, and uses the silicon hydrogen bonds as hydrogen donors to overcome oxygen inhibition, but the disadvantage is that the polysiloxane photoinitiator does not contain a photocurable group, and at the same time, the polysiloxane has extremely low surface energy, is easy to migrate to the surface of a photocurable material, and has migration problems in the photoinitiator.
Disclosure of Invention
In order to overcome the above-mentioned drawbacks and disadvantages of the prior art, a primary object of the present invention is to provide a low migration silicon-containing macroinitiator.
The invention also aims to provide a preparation method of the low-migration silicon-containing macromolecular photoinitiator. The invention grafts the photoinitiator onto the organic silicon acrylic ester to form a silicon-containing macromolecular photoinitiator, and meanwhile, a plurality of acrylic ester groups in the organic silicon acrylic ester can participate in the photocuring process, so that the migration problem of the common photoinitiator is solved. Meanwhile, organic silicon is introduced into the photo-curing system, so that the hydrophobicity and heat resistance of the photo-curing film can be improved.
It is a further object of the present invention to provide the use of the low migration silicon-containing macroinitiator described above.
The aim of the invention is achieved by the following scheme:
a low-migration silicon-containing macromolecular photoinitiator has the following specific structure:
wherein n=25 to 50, r 1 Is one of the following structures:
R 2 is one of the following structures:
R 3 is one of the following structures:
the preparation method of the low-migration silicon-containing macromolecular photoinitiator comprises the following steps:
(1) Performing a first hydrosilylation reaction on the hydrogen-terminated polydimethylsiloxane and acrylic ester to obtain organic silicon acrylic ester; then adding isocyanate to perform condensation reaction to obtain isocyanate grafted organosilicon acrylic ester; and adding a photoinitiator to obtain the photoinitiator grafted isocyanate organosilicon acrylate, namely the low-migration silicon-containing macromolecular photoinitiator.
Or comprises the following steps:
(2) Firstly, reacting a photoinitiator with isocyanate to obtain photoinitiator grafted isocyanate; then adding acrylic ester to obtain a photoinitiator grafted isocyanate acrylic ester compound; and adding hydrogen-terminated polydimethylsiloxane to perform hydrosilylation reaction to obtain the low-migration silicon-containing macromolecular photoinitiator.
Preferably, in the preparation method of the low-migration silicon-containing macromolecular photoinitiator, the method (1) specifically comprises the following steps:
uniformly mixing hydrogen-terminated polydimethylsiloxane, acrylic ester, a catalyst 1, a polymerization inhibitor and a solvent, and heating to perform a first-step hydrosilylation reaction to obtain organic silicon acrylic ester; then adding isocyanate and a catalyst 2 to perform a second condensation reaction to obtain isocyanate grafted organosilicon acrylic ester; and adding a photoinitiator, and grafting the photoinitiator onto isocyanate organosilicon acrylic ester to obtain the silicon-containing macromolecular photoinitiator.
The hydrogen-terminated polydimethylsiloxane has the structural formula H (CH) 3 ) 2 SiO[(CH 3 ) 2 SiO]nSi(CH 3 ) 2 H, mn=2000-4000; the acrylic ester is one of pentaerythritol triacrylate or dipentaerythritol pentaacrylate; the catalyst 1 is at least one of Karstedt catalyst or Spiecer catalyst; the polymerization inhibitor is at least one of hydroquinone, p-methoxyphenol, o-methyl hydroquinone, p-tert-butyl catechol and p-benzoquinone; the solvent is at least one of toluene and isopropanol;
the ratio of the amount of the hydrogen-terminated polydimethylsiloxane to the acrylate is 1:2 to 1:2.5, preferably 1:2; the concentration of the catalyst 1 is 4-20ppm, preferably 10ppm, and the ppm represents the mass of the catalyst 1 accounting for the weight percentage of the total mass of reactants; the mass of the polymerization inhibitor is 0.01% -0.1% of the total mass of reactants, and is preferably 0.1%; the mass of the solvent is 50% -150% of the total mass of the reactants, preferably 50%; wherein the total mass of reactants is the total mass of hydrogen terminated polydimethylsiloxane and acrylate.
The reaction condition of the first step of hydrosilylation reaction is that the reaction is carried out for 4 to 8 hours at the temperature of 80 to 110 ℃, preferably for 6 hours at the temperature of 100 ℃.
The isocyanate is diisocyanate and comprises one of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene Diisocyanate (XDI), hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and dicyclohexylmethane diisocyanate (HMDI);
the catalyst 2 is at least one of tertiary amines, metal compounds and organic phosphorus, and comprises at least one of triethanolamine, triethylenediamine, dibutyl tin dilaurate, stannous octoate, cobalt octoate, lead octoate and zinc naphthenate.
The dosage of the isocyanate is as follows: the ratio of the amounts of isocyanate and acrylate in the first hydrosilylation reaction was 1:1;
the reaction condition of the second condensation reaction is 35-45 ℃ for 3-5 hours, preferably 40 ℃ for 4 hours.
The photoinitiator refers to an alpha-hydroxy ketone derivative and comprises one of 2-hydroxy-2-methyl-propiophenone (Darocur 1173), 1-hydroxy-cyclohexyl propiophenone (Irgacure 184) and 2-hydroxy-2-methyl-p-hydroxyethyl ether propiophenone (Darocur 2959);
the grafting of the photoinitiator onto the isocyanate organosilicon acrylate means that the reaction is carried out for 3 to 6 hours at 60 to 80 ℃, preferably for 4 hours at 70 ℃.
And grafting the photoinitiator onto isocyanate organic silicon acrylic ester, and then removing the solvent by spin evaporation to obtain the silicon-containing macromolecular photoinitiator.
The dosages of the isocyanate, the photoinitiator and the catalyst 2 are as follows: the ratio of isocyanate to photoinitiator mass is 1:1; the mass of the catalyst 2 is 0.01% -0.1% of the total mass of reactants (reactants including acrylate, isocyanate and photoinitiator), preferably 0.1%.
The application of the low-migration silicon-containing macromolecular photoinitiator in the field of free radical photo-curing systems can initiate common acrylate reactive diluents and various acrylic resins.
The acrylic acid ester reactive diluent refers to a reactive monomer with at least one acrylic acid ester group, and comprises at least one of butyl acrylate, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate.
The acrylic resin refers to a polymer containing acrylate groups, and comprises at least one of unsaturated polyester, epoxy acrylic resin, polyurethane acrylic resin, polyester acrylic resin, polyether acrylic resin, acrylic acid ester resin or vinyl resin.
Compared with the prior art, the invention has the following advantages:
the photo-initiator is grafted to the organic silicon acrylic ester, so that the photo-curing agent becomes a silicon-containing macromolecular photo-initiator which is suitable for a free radical photo-curing system and can initiate common acrylic ester reactive diluents and various acrylic resins. The silicon-containing macromolecular photoinitiator has a plurality of acrylate groups, can participate in the photocuring process, and solves the migration problem of the common photoinitiator. Meanwhile, the organic silicon is introduced into the photo-curing system, so that the hydrophobicity and heat resistance of the photo-curing film can be improved.
Drawings
FIG. 1 is an infrared spectrum of a silicon-containing macromolecular photoinitiator prepared in example 1.
FIG. 2 is an infrared spectrum of the silicon-containing macromolecular photoinitiator prepared in example 4.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The hydrogen-terminated polydimethylsiloxanes used in the present invention were purchased from Guangdong Weng Jiang chemical company, inc.; the acrylic resin is epoxy acrylate (JZ-101) of Jining Hua Kai resin Co., ltd; the Spiecer catalyst is self-made and the preparation method is as follows: 0.1328g of chloroplatinic acid hexahydrate and 50.00g isopropanol are accurately weighed, placed in a beaker, stirred for 1 hour, and filled into a 100mL brown bottle for storage for later use. Other materials or instruments to which the present invention relates are commercially available. For process parameters not specifically noted, reference may be made to conventional techniques.
The reagents used in the examples are commercially available as usual unless otherwise specified.
Example 1
Hydrogen-terminated polydimethylsiloxane (20.00 g, mn=2000, pentaerythritol triacrylate (5.96 g) in a mass ratio of 1:2, spier catalyst (0.26 g), p-methoxyphenol (0.03 g), toluene (12.98 g) were added into a reaction vessel, stirred uniformly, and then heated to 100 ℃ for reaction for 6 hours, and the first hydrosilylation reaction was carried out. Then cooling the system to 40 ℃, adding 4.44g isophorone diisocyanate and 0.01g dibutyltin dilaurate, reacting for 4 hours, adding 3.28g 2-hydroxy-2-methyl-propiophenone (Darocur 1173), heating to 70 ℃, reacting for 4 hours, and removing the solvent by rotary evaporation after finishing the reaction to obtain the silicon-containing macromolecule photoinitiator with the mass of 32.82g. The mass of the prepared macromolecular photoinitiator is 32.82 g/3.28 g=10 times of the mass of Darocur1173 type, namely 2 parts of Darocur1173 type small molecular photoinitiator corresponds to 20 parts of macromolecular photoinitiator prepared in the example 1.
FIG. 1 is an infrared spectrum of the silicon-containing macromolecular photoinitiator prepared in example 1, as can be seen in FIG. 1: 2128cm -1 And 909cm -1 The disappearance of the Si-H peak at the site indicates the progress of the hydrosilylation reaction. 1731cm -1 C=o peak at and 1632cm -1 The c=c peak at this point appears, indicating the introduction of acrylate groups. 3360cm -1 The absorption peak of N-H appears at 1531cm -1 A strong N-H deformation vibration peak was also found at 2246cm -1 No absorption peak of-NCO at 1580cm -1 And 1441cm -1 The presence of benzene rings is indicated by the absorption peaks of (2) indicating that the reaction proceeds as expected and that the photoinitiator is successfully grafted to the polydimethylsiloxane segment.
Example 2
30.00g of hydrogen-terminated polydimethylsiloxane, 5.96g of pentaerythritol triacrylate with Mn=3000, the mass ratio of the two substances being 1:2, 0.36g of Spier catalyst, 0.04g of p-methoxyphenol and 17.98g of toluene are added into a reaction vessel, and after being stirred uniformly, the temperature is raised to 100 ℃ for reaction for 6 hours, and the first-step hydrosilylation reaction is carried out. Then cooling the system to 40 ℃, adding 4.44g isophorone diisocyanate and 0.01g dibutyltin dilaurate, reacting for 4 hours, adding 3.28g 2-hydroxy-2-methyl-propiophenone (Darocur 1173), heating to 70 ℃, reacting for 4 hours, and removing the solvent by rotary evaporation after finishing the reaction to obtain the silicon-containing macromolecule photoinitiator with the mass of 42.64g. The mass of the prepared macromolecular photoinitiator is 42.64 g/3.28 g=13 times that of the Darocur1173 type, namely 2 parts of Darocur1173 type small molecular photoinitiator corresponds to 26 parts of macromolecular photoinitiator prepared in the example 2.
Example 3
Hydrogen-terminated polydimethylsiloxane (40.00 g, mn=4000, pentaerythritol triacrylate (5.96 g) in a mass ratio of 1:2, spier catalyst (0.46 g), p-methoxyphenol (0.05 g) and toluene (22.98 g) are added into a reaction vessel, stirred uniformly, heated to 100 ℃ and reacted for 6 hours to perform a first hydrosilylation reaction. Then cooling the system to 40 ℃, adding 4.44g isophorone diisocyanate and 0.01g dibutyltin dilaurate, reacting for 4 hours, adding 3.28g 2-hydroxy-2-methyl-propiophenone (Darocur 1173), heating to 70 ℃, reacting for 4 hours, and removing the solvent by rotary evaporation after finishing the reaction to obtain the silicon-containing macromolecule photoinitiator with the mass of 52.48g. The mass of the prepared macromolecular photoinitiator is 52.48 g/3.28 g=16 times that of Darocur1173 type, namely 2 parts of Darocur1173 type small molecular photoinitiator corresponds to 32 parts of macromolecular photoinitiator prepared in the example 3.
Example 4
Hydrogen-terminated polydimethylsiloxane (20.00 g, mn=2000, pentaerythritol triacrylate (5.96 g) in a mass ratio of 1:2, spier catalyst (0.26 g), p-methoxyphenol (0.03 g), toluene (12.98 g) were added into a reaction vessel, stirred uniformly, and then heated to 100 ℃ for reaction for 6 hours, and the first hydrosilylation reaction was carried out. Then cooling the system to 40 ℃, adding 4.44g of isophorone diisocyanate and 0.01g of dibutyltin dilaurate, reacting for 4 hours, adding 4.08g of 1-hydroxy-cyclohexyl propiophenone (Irgacure 184), heating to 70 ℃, reacting for 4 hours, and removing the solvent by rotary evaporation after finishing the reaction to obtain the silicon-containing macromolecular photoinitiator with the mass of 32.64g. The mass of the prepared macromolecular photoinitiator is 32.64 g/4.08g=8 times of the mass of Irgacure184 type, namely 2 parts of Irgacure184 type small molecular photoinitiator corresponds to 16 parts of macromolecular photoinitiator prepared in the example 4.
FIG. 2 is an infrared spectrum of the silicon-containing macroinitiator prepared in example 4, as can be seen from FIG. 2: 2128cm -1 And 909cm -1 The disappearance of the Si-H peak at the site indicates the progress of the hydrosilylation reaction. 1731cm -1 C=o peak at and 1632cm -1 The c=c peak at this point appears, indicating the introduction of acrylate groups. 3360cm -1 The absorption peak of N-H appears at 1531cm -1 A strong N-H deformation vibration peak was also found at 2246cm -1 No absorption peak of-NCO at 1580cm -1 And 1441cm -1 The presence of benzene rings is indicated by the absorption peaks of (2) indicating that the reaction proceeds as expected and that the photoinitiator is successfully grafted to the polydimethylsiloxane segment.
Example 5
Hydrogen-terminated polydimethylsiloxane (20.00 g, mn=2000, pentaerythritol triacrylate (5.96 g) in a mass ratio of 1:2, spier catalyst (0.26 g), p-methoxyphenol (0.03 g), toluene (12.98 g) were added into a reaction vessel, stirred uniformly, and then heated to 100 ℃ for reaction for 6 hours, and the first hydrosilylation reaction was carried out. Then cooling the system to 40 ℃, adding 4.44g isophorone diisocyanate and 0.01g dibutyltin dilaurate, reacting for 4 hours, adding 4.48g 2-hydroxy-2-methyl-p-hydroxyethyl ether-propiophenone (Darocur 2959), heating to 70 ℃, reacting for 4 hours, and removing the solvent by rotary evaporation after finishing the reaction, thus obtaining the silicon-containing macromolecular photoinitiator with the mass of 33.60g. The mass of the prepared macromolecular photoinitiator is 33.60 g/4.48 g=7.5 times that of the Darocur2959 type, namely 2 parts of Darocur2959 type small molecular photoinitiator corresponds to 15 parts of the macromolecular photoinitiator prepared in the example 5.
Example 6
Hydrogen-terminated polydimethylsiloxane (20.00 g, mn=2000, dipentaerythritol pentaacrylate (10.49 g) and Spiecer catalyst (0.30 g, p-methoxyphenol (0.03 g), toluene (15.25 g) are added into a reaction vessel, stirred uniformly, heated to 100 ℃ and reacted for 6 hours, and the first hydrosilylation reaction is carried out. Then cooling the system to 40 ℃, adding 4.44g isophorone diisocyanate and 0.02g dibutyltin dilaurate, reacting for 4 hours, adding 3.28g 2-hydroxy-2-methyl-propiophenone (Darocur 1173), heating to 70 ℃, reacting for 4 hours, and removing the solvent by rotary evaporation after finishing the reaction to obtain the silicon-containing macromolecule photoinitiator with the mass of 36.08g. The mass of the prepared macromolecular photoinitiator is 36.08 g/3.28 g=11 times that of Darocur1173 type, namely 2 parts of Darocur1173 type small molecular photoinitiator corresponds to 22 parts of macromolecular photoinitiator prepared in the example 6.
Example 7
30.00g of hydrogen-terminated polydimethylsiloxane, 10.49g of dipentaerythritol pentaacrylate and the mass ratio of 1:2, 0.40g of Spiecer catalyst, 0.04g of p-methoxyphenol and 20.25g of toluene are added into a reaction vessel, and after uniform stirring, the temperature is raised to 100 ℃ for reaction for 6 hours, and the first-step hydrosilylation reaction is carried out. Then cooling the system to 40 ℃, adding 4.44g isophorone diisocyanate and 0.02g dibutyltin dilaurate, reacting for 4 hours, adding 3.28g 2-hydroxy-2-methyl-propiophenone (Darocur 1173), heating to 70 ℃, reacting for 4 hours, and removing the solvent by rotary evaporation after finishing the reaction to obtain the silicon-containing macromolecule photoinitiator with the mass of 45.92g. The mass of the prepared macromolecular photoinitiator is 45.92 g/3.28 g=14 times of the mass of Darocur1173 type, namely 2 parts of Darocur1173 type small molecular photoinitiator corresponds to 28 parts of macromolecular photoinitiator prepared in the example 7.
Example 8
Hydrogen-terminated polydimethylsiloxane (40.00 g, mn=4000, dipentaerythritol pentaacrylate (10.49 g) in a mass ratio of 1:2, spier catalyst (0.50 g), p-methoxyphenol (0.05 g), toluene (25.25 g) were added into a reaction vessel, stirred uniformly, heated to 100 ℃ and reacted for 6 hours, and the first hydrosilylation reaction was carried out. Then cooling the system to 40 ℃, adding 4.44g isophorone diisocyanate and 0.02g dibutyltin dilaurate, reacting for 4 hours, adding 3.28g 2-hydroxy-2-methyl-propiophenone (Darocur 1173), heating to 70 ℃, reacting for 4 hours, and removing the solvent by rotary evaporation after finishing the reaction to obtain the silicon-containing macromolecule photoinitiator with the mass of 55.76g. The mass of the prepared macromolecular photoinitiator is 55.76 g/3.28 g=17 times of the mass of Darocur1173 type, namely 2 parts of Darocur1173 type small molecular photoinitiator corresponds to 34 parts of macromolecular photoinitiator prepared in the example 8.
Example 9
Hydrogen-terminated polydimethylsiloxane (20.00 g, mn=2000, dipentaerythritol pentaacrylate (10.49 g) and Spiecer catalyst (0.30 g, p-methoxyphenol (0.03 g), toluene (15.25 g) are added into a reaction vessel, stirred uniformly, heated to 100 ℃ and reacted for 6 hours, and the first hydrosilylation reaction is carried out. Then cooling the system to 40 ℃, adding 4.44g of isophorone diisocyanate and 0.02g of dibutyltin dilaurate, reacting for 4 hours, adding 4.08g of 1-hydroxy-cyclohexyl propiophenone (Irgacure 184), heating to 70 ℃, reacting for 4 hours, and removing the solvent by rotary evaporation after finishing the reaction to obtain the silicon-containing macromolecular photoinitiator with the mass of 36.72g. The mass of the prepared macromolecular photoinitiator is 36.72 g/4.08g=9 times of the mass of Irgacure184 type, namely 2 parts of Irgacure184 type small molecular photoinitiator corresponds to 18 parts of the macromolecular photoinitiator prepared in the example 9.
Example 10
Hydrogen-terminated polydimethylsiloxane (20.00 g, mn=2000, dipentaerythritol pentaacrylate (10.49 g) and Spiecer catalyst (0.30 g, p-methoxyphenol (0.03 g), toluene (15.25 g) are added into a reaction vessel, stirred uniformly, heated to 100 ℃ and reacted for 6 hours, and the first hydrosilylation reaction is carried out. Then cooling the system to 40 ℃, adding 4.44g isophorone diisocyanate and 0.02g dibutyltin dilaurate, reacting for 4 hours, adding 4.48g 2-hydroxy-2-methyl-p-hydroxyethyl ether-propiophenone (Darocur 2959), heating to 70 ℃, reacting for 4 hours, and removing the solvent by rotary evaporation after finishing the reaction, thus obtaining the silicon-containing macromolecular photoinitiator with the mass of 38.08g. The mass of the prepared macromolecular photoinitiator is 38.08 g/4.48 g=8.5 times that of the Darocur2959 type, namely 2 parts of Darocur2959 type small molecular photoinitiator corresponds to 17 parts of the macromolecular photoinitiator prepared in the example 10.
To illustrate that the prepared silicon-containing macromolecular photoinitiator has the effect of the photoinitiator and the low migration effect, and can improve the hydrophobicity and the heat resistance of the material, the silicon-containing macromolecular photoinitiator prepared in the embodiment is selected to be compared with Darocur1173, irgacure184 and Darocur 2959; the selected acrylic acid ester reactive diluents are 1, 6-hexanediol diacrylate and trimethylolpropane triacrylate. The acrylic resin is epoxy acrylate (JZ-101) of Jining Hua Kai resin Co.
The photo-curing formula comprises the following raw materials in parts by weight:
raw materials are weighed according to the above formula and table 1, uniformly stirred, then coated on a substrate (paper, glass, steel plate, etc.) by using a 20-micrometer bar, and then covered with a layer of PET film to isolate oxygen, and photo-cured under a mercury lamp of 2 kilowatts for 5 seconds.
The amount of photoinitiator added and the corresponding photo-curing time and material properties are shown in table 1 below:
TABLE 1 addition of photoinitiators and corresponding photo-curing times and Material Properties
The mobility test method comprises the following steps: taking a glass substrate as an example, firstly weighing the mass of a glass plate, and then weighing the mass of the glass plate containing the cured film, wherein the mass difference between the two is the mass m of the cured film loaded on the glass plate 1 . The glass plate containing the cured film was then immersed in a brown jar containing 50ml of chloroform extract for 4 days. After the soaking is finished, the UV absorption spectrum is tested. Calculating the concentration of the residual photoinitiator in the chloroform extract according to the lambert beer law, and obtaining the mass m of the residual photoinitiator 2 . Mobility=m 2 /m 1 。
The hydrophobic angle is a contact angle measured by a common contact angle meter on the market by using water as a liquid, and the hydrophobic angle is more than 90 degrees, which indicates that the water-repellent material has good hydrophobicity;
the heat resistance is data obtained by measuring the weight loss relationship of the cured film by a Metler thermal analyzer (Mettler TGA/DSC), where T 5％ T represents the temperature at which the cured film loses 5% of weight max The temperature at which the rate of weight loss of the cured film was maximum was shown. The test conditions were nitrogen atmosphere, and the temperature was increased from 30℃to 800℃at a rate of 10℃per minute.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (14)
1. A low-migration silicon-containing macromolecular photoinitiator is characterized by having the following structural formula:
；
wherein n=25 to 50, R 1 Is one of the following structures:
；
R 2 is one of the following structures:
；
R 3 is one of the following structures:
。
2. a method of preparing a low migration silicon-containing macroinitiator of claim 1, comprising the steps of:
performing a first hydrosilylation reaction on the hydrogen-terminated polydimethylsiloxane and acrylic ester to obtain organic silicon acrylic ester; then adding isocyanate to perform condensation reaction to obtain isocyanate grafted organosilicon acrylic ester; and adding a photoinitiator to obtain the photoinitiator grafted isocyanate organosilicon acrylate, namely the low-migration silicon-containing macromolecular photoinitiator.
3. The method for preparing the low-migration silicon-containing macromolecular photoinitiator according to claim 2, comprising the following steps:
uniformly mixing hydrogen-terminated polydimethylsiloxane, acrylic ester, a catalyst 1, a polymerization inhibitor and a solvent, and heating to perform a first-step hydrosilylation reaction to obtain organic silicon acrylic ester; then adding isocyanate and a catalyst 2 to perform a second condensation reaction to obtain isocyanate grafted organosilicon acrylic ester; and adding a photoinitiator, and grafting the photoinitiator onto isocyanate organosilicon acrylate to obtain the silicon-containing macromolecular photoinitiator.
4. A method of preparing a low migration silicon-containing macroinitiator according to claim 3, wherein:
the reaction condition of the first-step hydrosilylation reaction is that the reaction is carried out for 4-8 hours at the temperature of 80-110 ℃;
the reaction condition of the second condensation reaction is 35-45 ℃ for 3-5 hours;
the grafting of the photoinitiator onto the isocyanate organosilicon acrylate means that the reaction is carried out for 3 to 6 hours at the temperature of 60 to 80 ℃.
5. The method for preparing the low-migration silicon-containing macromolecular photoinitiator according to claim 4, wherein the method comprises the following steps:
the reaction condition of the first step of hydrosilylation reaction is that the reaction is carried out for 6 hours at 100 ℃;
the reaction condition of the second condensation reaction is that the reaction is carried out for 4 hours at 40 ℃;
grafting the photoinitiator onto the isocyanate organosilicon acrylate refers to reacting for 4 hours at 70 ℃.
6. A method of preparing a low migration silicon-containing macroinitiator according to claim 3, wherein:
the hydrogen-terminated polydimethylsiloxane has the structural formula H (CH) 3 ) 2 SiO[(CH 3 ) 2 SiO]nSi(CH 3 ) 2 H，Mn=2000-4000；
The acrylic ester is one of pentaerythritol triacrylate or dipentaerythritol pentaacrylate;
the catalyst 1 is at least one of Karstedt catalyst or Spiecer catalyst;
the polymerization inhibitor is at least one of hydroquinone, p-methoxyphenol, o-methyl hydroquinone, p-tert-butyl catechol and p-benzoquinone;
the solvent is at least one of toluene and isopropanol;
the ratio of the hydrogen-terminated polydimethylsiloxane to the acrylate is 1:2-1:2.5; catalyst 1 concentration is 4 to 20ppm, ppm representing the mass of catalyst 1 as a percentage of the total mass of reactants, the total mass of reactants being the total mass of hydrogen terminated polydimethylsiloxane and acrylate.
7. The method for preparing the low-migration silicon-containing macromolecular photoinitiator according to claim 6, wherein the method comprises the following steps:
the ratio of the amount of the hydrogen-terminated polydimethylsiloxane to the amount of the acrylate is 1:2; the catalyst 1 concentration was 10ppm, which indicates the mass of catalyst 1 as a percentage of the total mass of reactants, which is the total mass of hydrogen-terminated polydimethylsiloxane and acrylate.
8. A method of preparing a low migration silicon-containing macroinitiator according to claim 3, wherein:
the isocyanate is diisocyanate and comprises one of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate;
the catalyst 2 is at least one of tertiary amines, metal compounds and organic phosphorus;
the dosage of the isocyanate is as follows: the ratio of the amounts of isocyanate and acrylate in the first hydrosilylation reaction was 1:1.
9. The method for preparing the low-migration silicon-containing macromolecular photoinitiator according to claim 8, wherein the method comprises the following steps:
the catalyst 2 comprises at least one of triethanolamine, triethylenediamine, dibutyltin dilaurate, stannous octoate, cobalt octoate, lead octoate and zinc naphthenate.
10. A method of preparing a low migration silicon-containing macroinitiator according to claim 3, wherein:
the photoinitiator refers to an alpha-hydroxy ketone derivative and comprises one of 2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl propiophenone and 2-hydroxy-2-methyl-p-hydroxyethyl ether propiophenone;
the dosages of the isocyanate, the photoinitiator and the catalyst 2 are as follows: the ratio of isocyanate to photoinitiator mass is 1:1; the mass of the catalyst 2 is 0.01% -0.1% of the total mass of reactants, wherein the reactants comprise acrylic ester, isocyanate and photoinitiator.
11. A method of preparing a low migration silicon-containing macroinitiator according to claim 3, wherein:
the dosages of the isocyanate, the photoinitiator and the catalyst 2 are as follows: the ratio of isocyanate to photoinitiator mass is 1:1; the mass of the catalyst 2 is 0.1% of the total mass of reactants, wherein the reactants comprise acrylic ester, isocyanate and photoinitiator.
12. Use of a low migration silicon-containing macroinitiator according to claim 1 in the field of free radical photocuring systems.
13. Use of a low migration, silicon-containing macroinitiator according to claim 12 in the field of free radical photocuring systems, characterized in that: the low migration silicon-containing macroinitiator is capable of initiating acrylate reactive diluents and acrylic resins.
14. Use of a low migration, silicon-containing macroinitiator according to claim 13 in the field of free radical photo-curing systems, characterized in that:
the acrylic acid ester reactive diluent refers to a reactive monomer with at least one acrylic acid ester group, and comprises at least one of butyl acrylate, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate;
the acrylic resin refers to a polymer containing acrylate groups, and comprises at least one of unsaturated polyester, epoxy acrylic resin, polyurethane acrylic resin, polyester acrylic resin, polyether acrylic resin, acrylic acid ester resin or vinyl resin.
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| CN111234773A (en) * | 2020-03-10 | 2020-06-05 | 烟台德邦科技有限公司 | Silicone sealant with high environmental adaptability |
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2021
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| GB2100722A (en) * | 1981-06-18 | 1983-01-06 | Nat Starch Chem Corp | Monomeric carbamic ester photoinitiators |
| CN1817915A (en) * | 2006-01-24 | 2006-08-16 | 武汉大学 | Cracking light initiating agent containing high-molecular chain segment, its production and use |
| CN102408500A (en) * | 2010-09-21 | 2012-04-11 | 北京化工大学 | Novel siliceous macro-molecule photoinitiator and its preparation method |
| CN108504269A (en) * | 2018-03-26 | 2018-09-07 | 华南理工大学 | A kind of floride-free nonpolluting coating and preparation method thereof of ultraviolet light/sun light curable |
| CN111234773A (en) * | 2020-03-10 | 2020-06-05 | 烟台德邦科技有限公司 | Silicone sealant with high environmental adaptability |
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